Resin composition and manufacturing method of coating layer using the same

ABSTRACT

each of Y1 to Y4 is H or OH—, at least one of Y1 and Y2 is OH—, at least one of Y3 and Y4 is OH—, each of X1 to X3 is independently a C1-C20 alkyl group, the alkyl group includes or does not include an unsaturated bond, —CH2— in the alkyl group may be substituted or unsubstituted with —CHOH—, and each of n and m is independently 1 to 200.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2017-0056526 filed in the Korean IntellectualProperty Office on May 2, 2017, the entire contents of which areincorporated herein by reference.

BACKGROUND 1. Field

Embodiments of the present disclosure relate to a resin composition anda manufacturing method of a coating layer using the resin composition.

2. Description of the Related Art

Recently, various kinds of display devices have been developed. A flatpanel display generally includes a liquid crystal display (LCD), anorganic light emitting diode (OLED) display, an electrophoretic display(EPD), and the like.

The flat panel display devices may transmit a clear image to a userwithout distortion. Therefore, a window laminated on the flat paneldisplay may have high transmittance and flatness. In addition, as thenumber of a portable flat panel displays such as a smart phone or atablet PC increases, the flat panel display may be frequently exposed toan external impact. Therefore, a flat panel display should be capable ofwithstanding an external impact.

In order to protect the flat panel display, various films may belaminated on a window of the flat panel display. In a manufacturingprocess, these films may be peeled off and then reattached after beingformed on the window. While the film is reattached, bubbles may beinserted or form between the film and the window. Such a bubbleinsertion or formation may deteriorate aesthetic impression andvisibility of the flat panel display.

SUMMARY

An exemplary embodiment of the present disclosure provides a resincomposition for forming a coating layer having excellent bubble-freeproperty in which bubbles are not inserted between a substrate and thecoating layer when the substrate and the coating layer are reattachingafter peeling.

In addition, an exemplary embodiment of the present disclosure providesa manufacturing method of a coating layer for forming a coating layerhaving excellent bubble-free property by using the resin composition.

According to an exemplary embodiment of the present disclosure, a resincomposition includes first polyol represented by Chemical Formula 1,second polyol represented by Chemical Formula 2, and polyisocyanate,wherein the first polyol and the second polyol have a linear structurewithout a side chain.

each of Y₁ to Y₄ is H or OH—, at least one of Y₁ and Y₂ is OH—, at leastone of Y₃ and Y₄ is OH—, each of X₁ to X₃ is independently a C1-C20alkyl group, the alkyl group includes or does not include an unsaturatedbond, —CH₂— in the alkyl group may be substituted or unsubstituted with—CHOH—, and each of n and m is independently 1 to 200.

According to an exemplary embodiment of the present disclosure, theresin composition may further include a curing agent and antistaticagent, wherein the curing agent includes isocyanate.

According to an exemplary embodiment of the present disclosure, thecuring agent may include a mixture of dodecanedioic acid and triglycidylisocyanurate.

According to an exemplary embodiment of the present disclosure, theantistatic agent may include a compound represented by Chemical Formula3.

M-A  Chemical Formula 3

M is a metal element, and A is at least one selected from a chlorideanion (Cl⁻), a bromide anion (Br⁻), an iodide anion (I⁻), atetrachloroaluminate anion (AlCl₄ ⁻), a heptachlorodialuminate anion(Al₂Cl₇ ⁻), a tetrafluoroborate anion (BF₄ ⁻), a hexafluorophosphateanion (PF₆ ⁻), a perchlorate anion (ClO₄ ⁻), a nitrate anion (NO₃ ⁻), anacetate anion (CH₃COO⁻), a trifluoroacetate anion (CF₃COO⁻), a methanesulfonate anion (CH₃SO₃ ⁻), a trifluoromethanesulfonate anion (CF₃SO₃⁻), a p-toluenesulfonate anion (p-CH₃C₆H₄SO₃ ⁻), a bis (fluorosulfonyl)imide anion ((FSO₂₂N⁻), a bis (trifluoromethanesulfonyl) imide anion((CF₃SO₂)₂N⁻), a tris (trifluoromethanesulfonyl) (CF₃SO₂)₃C⁻), ahexafluoroacenate anion (AsF₆ ⁻), a hexafluoroantimonate anion (SbF₆ ⁻),a hexafluoroniobate anion (NbF₆ ⁻), a hexafluorotantalate anion (TaF₆⁻), dimethylphosphinate (CH₃₂POO⁻), a dicyanamide anion ((CN)₂N⁻), athiocyanic anion (SCN⁻), a perfluorobutane sulfonate anion (C₄F₉SO₃ ⁻),a bis (pentafluoroethanesulfonyl) imide anion ((C₂F₅SO₂)₂N⁻) and aperfluorobutanoate anion (C₃F₇COO⁻).

According to an exemplary embodiment of the present disclosure, theantistatic agent may be a lithium-based antistatic agent including alithium element.

According to an exemplary embodiment of the present disclosure, theresin composition may further include a tin-based catalyst.

According to an exemplary embodiment of the present disclosure, theresin composition includes 10 to 20 parts by weight of the secondpolyol, and 3 to 8 parts by weight of the polyisocyanate, with respectto 100 parts by weight of the first polyol.

According to an exemplary embodiment of the present disclosure, theresin composition may further include at least one solvent selected fromthe group consisting of toluene, acetone, cyclohexanone, ethylcellusolve, ethyl acetate, isopropyl alcohol, and ethylene glycolmonomethyl ether.

According to an exemplary embodiment of the present disclosure, theresin composition may further include a heat stabilizer, wherein theheat stabilizer may be a phenolic compound, a phospho compound, or athio compound.

According to an exemplary embodiment of the present disclosure, amanufacturing method of a coating layer includes forming a resincomposition by mixing first polyol represented by Chemical Formula 1,second polyol represented by Chemical Formula 2, and polyisocyanatetogether with a first solvent, coating the resin composition on asubstrate, and aging the resin composition, wherein the first polyol andthe second polyol have a linear structure without a side chain.

each of Y₁ to Y₄ is H or OH—, at least one of Y₁ and Y₂ is OH—, at leastone of Y₃ and Y₄ is OH—, each of X₁ to X₃ is independently a C1-C20alkyl group, the alkyl group includes or does not include an unsaturatedbond, —CH₂— in the alkyl group may be substituted or unsubstituted with—CHOH—, and each of n and m is independently 1 to 200.

According to an exemplary embodiment of the present disclosure, formingthe resin composition may further include mixing a mixture of a secondsolvent different from the first solvent, a curing agent and anantistatic agent mixture with a mixture of the first polyol, the secondpolyol, the polyisocyanate and the first solvent.

According to an exemplary embodiment of the present disclosure, themanufacturing method of a coating layer may further include heating themixture of the first polyol, the second polyol, the polyisocyanate andthe first solvent to remove isocyanate bonds in the mixture of the firstpolyol, the second polyol, the polyisocyanate, and the first solvent.

According to an exemplary embodiment of the present disclosure, themixture of the first polyol, the second polyol, the polyisocyanate andthe first solvent may be heated at 60° C. to 90° C.

According to an exemplary embodiment of the present disclosure, a heatstabilizer may be added to the heated mixture of the first polyol, thesecond polyol, the polyisocyanate and the first solvent.

According to an exemplary embodiment of the present disclosure, agingthe resin composition may include heating the resin composition at 40°C. to 140° C.

According to an exemplary embodiment of the present disclosure, agingthe resin composition may include a plurality of heating acts.

According to an exemplary embodiment of the present disclosure, agingthe resin composition may include a first heating act, a second heatingact, a third heating act, a fourth heating act, and a fifth heating act.

According to an exemplary embodiment of the present disclosure, aprocess temperature of the first heating act to the third heating act isless than a process temperature of the fourth heating act and the fifthheating act.

According to an exemplary embodiment of the present disclosure, a resincomposition having excellent bubble-free property and free fromsubstrate contamination may be provided.

However, the effects of embodiments of the present disclosure are notlimited to the above-described effects, and may be variously extendedwithout departing from the spirit and scope of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, together with the specification, illustrateembodiments of the subject matter of the present disclosure, and,together with the description, serve to explain principles ofembodiments of the subject matter of the present disclosure.

FIG. 1 is a flowchart illustrating a manufacturing method of a coatinglayer according to an exemplary embodiment of the present disclosure.

FIG. 2 is a flowchart illustrating a forming method of a resincomposition according to an exemplary embodiment of the presentdisclosure.

FIG. 3 shows an aging apparatus for performing a first heating act to asixth heating act.

DETAILED DESCRIPTION

It will be apparent to those skilled in the art that variousmodifications and variations can be made to the subject matter of thepresent disclosure without departing from the spirit or scope of thedisclosure, and certain exemplary embodiments are exemplified in thedrawings and explained in the detailed description. Thus, it is intendedthat the present disclosure covers modifications and variations of thesubject matter of the present disclosure included within the spirit andscope of the present disclosure and their equivalents.

Like reference numerals designate like elements throughout thespecification. In the accompanying drawings, dimensions of structuresare exaggerated for clarity. The terms, ‘first’, ‘second’ and the likemay be simply used for description of various constituent elements, butthose meanings may not be limited to the restricted meanings. The aboveterms are used only for distinguishing one constituent element fromother constituent elements. For example, a first constituent element maybe referred to as a second constituent element and similarly, the secondconstituent element may be referred to as the first constituent elementwithin the scope of the appended claims, and equivalents thereof. Whenexplaining the singular, unless explicitly described to the contrary, itmay be interpreted to also have the plural meaning.

In the specification and claims, the word “comprise” or “has” is used tospecify existence of a feature, a numbers, a process, an operation, aconstituent element, a part, or a combination thereof, and it will beunderstood that existence or additional possibility of one or more otherfeatures or numbers, processes, operations, constituent elements, parts,or combinations thereof are not excluded in advance. In addition, itwill be understood that when an element such as a layer, film, region,or substrate is referred to as being “on” another element, it can bedirectly on the other element or intervening elements may also bepresent. In the specification and claims, it will be understood thatwhen an element such as a layer, film, region, or substrate is referredto as being disposed “on” another element, the disposed direction is notlimited to an upper direction and include a side direction or a lowerdirection. In contrast, it will be understood that when an element suchas a layer, film, region, or substrate is referred to as being “beneath”another element, it can be directly beneath the other element orintervening elements may also be present.

In the present specification and claims, the terms ‘upper side’ and‘lower side’ are used in a relative sense in order to facilitateunderstanding of the technical idea of embodiments of the presentdisclosure. Thus, the terms ‘upper side’ and ‘lower side’ do not referto a particular direction, position, or element, and areinterchangeable. For example, ‘upper side’ may be interpreted as ‘lowerside’, and ‘lower side’ may be interpreted as ‘upper side’. Therefore,‘upper side’ may be expressed as ‘first side’, ‘lower side’ may beexpressed as ‘second side’, ‘lower side’ may be expressed as ‘firstside’, and ‘upper side’ may be expressed as ‘second side’. However, inone exemplary embodiment, ‘upper side’ and ‘lower side’ are not mixed(e.g., the terms are not interchangeable).

As used herein, the terms “substantially,” “about,” and similar termsare used as terms of approximation and not as terms of degree, and areintended to account for the inherent deviations in measured orcalculated values that would be recognized by those of ordinary skill inthe art. Further, the use of “may” when describing embodiments of thepresent disclosure refers to “one or more embodiments of the presentdisclosure.” As used herein, the terms “use,” “using,” and “used” may beconsidered synonymous with the terms “utilize,” “utilizing,” and“utilized,” respectively. Also, the term “exemplary” is intended torefer to an example or illustration.

Also, any numerical range recited herein is intended to include allsubranges of the same numerical precision subsumed within the recitedrange. For example, a range of “1.0 to 10.0” is intended to include allsubranges between (and including) the recited minimum value of 1.0 andthe recited maximum value of 10.0, that is, having a minimum value equalto or greater than 1.0 and a maximum value equal to or less than 10.0,such as, for example, 2.4 to 7.6. Any maximum numerical limitationrecited herein is intended to include all lower numerical limitationssubsumed therein, and any minimum numerical limitation recited in thisspecification is intended to include all higher numerical limitationssubsumed therein. Accordingly, Applicant reserves the right to amendthis specification, including the claims, to expressly recite anysub-range subsumed within the ranges expressly recited herein.

After a resin composition according to an exemplary embodiment of thepresent disclosure is coated on a substrate, the resin composition maybe aged so as to form a coating layer. The coating layer may be providedalone or with another film on the substrate. Thus, the resin compositionand the coating layer made from the resin composition may have adhesivecharacteristics for bonding the film to the substrate.

The resin composition according to an exemplary embodiment of thepresent disclosure does not include a silicone resin. In the existingart, a silicone resin has been used to improve a bubble-free property ofa coating layer or an adhesive layer.

Bubble free means that bubbles are not (or substantially not) insertedor formed between a coating layer and a substrate. For example, thebubble-free property means that bubbles are not (or substantially not)inserted or formed between the coating layer and the substrate, not onlywhen the coating layer is formed on the substrate, but also when theformed coating layer is peeled off from the substrate and thenreattached on the substrate. For example, the coating layer and thesubstrate may be completely free of bubbles (e.g., pockets of air orother gases) between the coating layer and the substrate.

As the coating layer or the adhesive layer has the bubble-free property,an adhesion of the coating layer to the substrate can be maintained evenif the coating layer and the substrate are repeatedly peeled and bonded.In addition, since there is no bubble between the substrate and thecoating layer, the coating layer can be more closely bonded to thesubstrate.

The coating layer or the adhesive layer including the existing siliconeresin may have excellent bubble-free properties because a surfacetension is relatively low. However, the coating layer or the adhesivelayer including the silicone resin substrate may contaminate thesubstrate. For example, a Si—O group in the silicone resin may chemisorbwith a surface of the substrate. In certain embodiments, when thesubstrate includes silicon together with glass, the Si—O group in thesilicone resin may react with the silicon on the surface of thesubstrate to form siloxane. If the silicone resin is chemisorbed on thesurface of the substrate, the surface of the substrate may becontaminated and the visibility may be deteriorated. Further, thephysical properties of the substrate may be changed to deteriorateimpact resistance and flexibility.

Since a resin composition according to an exemplary embodiment of thepresent disclosure does not include a silicone resin, the substrate isnot contaminated by chemisorption of the silicone resin.

In addition, a resin composition according to an exemplary embodiment ofthe present disclosure does not include a plasticizer. In the existingart, a plasticizer such as isopropyl myristate was added to the resincomposition to improve bubble-free property of the coating layer or theadhesive layer. The plasticizer imparts flexibility to the resincomposition and the coating layer or the adhesive layer made therefrom.Therefore, the resin composition including the plasticizer and thecoating layer or the adhesive layer made therefrom may have a relativelyexcellent bubble-free property. However, the plasticizer may betransferred from the coating layer or the adhesive layer to thesubstrate. The plasticizer may be easily transferred to the substratedue to good compatibility in general. The plasticizer transferred to thesubstrate may contaminate the substrate like the silicone resinchemisorbed on the substrate. Such contamination of the substrate maydeteriorate visibility and impact resistance.

Since a resin composition according to an exemplary embodiment of thepresent disclosure does not include a plasticizer, the substrate is notcontaminated by transition of the plasticizer.

The resin composition according to an exemplary embodiment of thepresent disclosure does not include a plasticizer or a silicone resin(e.g., the resin is free of a plasticizer and/or a silicone resin) buthas an excellent bubble-free property. For this purpose, a resincomposition according to an exemplary embodiment of the presentdisclosure may include a first polyol represented by Chemical Formula 1,a second polyol represented by Chemical Formula 2, and polyisocyanate,where the first polyol and the second polyol have a linear structurewithout a side chain.

Herein, each of Y₁ to Y₄ is H or OH—, at least one of Y₁ and Y₂ is OH—,at least one of Y₃ and Y₄ is OH—, each of X₁ to X₃ is independently aC1-C20 alkyl group, the alkyl group includes or does not include anunsaturated bond, —CH₂— in the alkyl group may be substituted orunsubstituted with —CHOH—, and each of n and m is independently 1 to200.

The first polyol may be a single material (e.g., a single or solechemical compound) or a mixture of two or more materials having astructure of Chemical Formula 1. For example, the first polyol mayinclude at least one selected from materials having a structure ofChemical Formula 1-1 to Chemical Formula 1-5. However, materials havinga structure of the Chemical Formula 1-1 to Chemical Formula 1-5 aremerely examples of materials that may be used as the first polyol, andthe structure of the first polyol is not limited to the Chemical Formula1-1 to Chemical Formula 1-5.

The second polyol may be a single material (e.g., a single or solechemical compound) or a mixture of two or more materials having astructure of Chemical Formula 2. For example, the second polyol mayinclude at least one selected from materials having a structure ofChemical Formula 2-1 to Chemical Formula 2-3. However, materials havinga structure of the Chemical Formula 2-1 to Chemical Formula 2-3 aremerely examples of materials that may be used as the second polyol, andthe structure of the second polyol is not limited to the ChemicalFormula 2-1 to Chemical Formula 2-3.

The first polyol and the second polyol have a linear structure without aside chain. Herein, the side chain means a group substituted withhydrogen existing in a main chain composed of a carbon-carbon bond.Since the first polyol and the second polyol according to an exemplaryembodiment of the present disclosure have a linear structure without aside chain, they may react with isocyanate to form a linear polymer. Forexample, the linear polymer may be a polyurethane resin. The linearpolymer may be flexible and wettability of the coating layer includingthe linear polymer may be improved because it has no side chains. As theflexibility and wettability of the coating layer are improved, thecoating layer may have a bubble-free property.

The first polyol may have a viscosity of about 0.85 pascal seconds(Pa·s) to about 1.35 Pa·s at about 20° C. The viscosity of the firstpolyol affects a viscosity of the resin composition including the firstpolyol. When the first polyol has a viscosity lower than the viscosityof the above range, a viscosity of the resin composition decreases sothat the resin composition coated on the substrate may flow down. On theother hand, when the first polyol has a viscosity higher than theviscosity of the above range, a viscosity of the resin compositionincreases, and it may be difficult to uniformly or substantiallyuniformly coat the resin composition.

The first polyol may have a hydroxyl value of about 25.0 mg KOH/g toabout 29.0 mg KOH/g. By having the hydroxyl value of the above range,the first polyol may react with other components in the resincomposition so as to provide a coating layer having an excellentbubble-free property.

The second polyol may have a density of about 1.05 g/ml to about 1.12g/ml at about 20° C. However, a density of the second polyol may changedepending on a form of the second polyol. For example, as a length of amain chain of the second polyol becomes longer, a density of the secondpolyol may be relatively low.

The second polyol may have a viscosity of about 0.15 Pa·s to about 0.19Pa·s at about 20° C. The viscosity of the second polyol affects aviscosity of the resin composition including the second polyol. When thesecond polyol has a viscosity lower than the viscosity of the aboverange, a viscosity of the resin composition decreases so that the resincomposition coated on the substrate may flow down. On the other hand,when the second polyol has a viscosity higher than the viscosity of theabove range, a viscosity of the resin composition increases, and it maybe difficult to uniformly or substantially uniformly coat the resincomposition.

The polyisocyanate may be a material including a plurality of isocyanategroups (—NCO). Examples of the polyisocyanate include aromaticisocyanate compounds such as 2,4-tolylene diisocyanate, 2,6-tolylenediisocyanate, 1,3-xylylene diisocyanate, 4,4′-diphenyl diisocyanate,1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, and thelike; compounds having two isocyanate groups bonded to alicyclichydrocarbons such as dicyclohexylmethane diisocyanate, isophoronediisocyanate, norbornane diisocyanate, hydrogenated xylylenediisocyanate, hydrogenated methylene bisphenylene diisocyanate,1,4-cyclohexane diisocyanate, and the like; and compounds having twoisocyanate groups bonded to aliphatic hydrocarbons such as trimethylenediisocyanate, hexamethylene diisocyanate, and the like. Thesepolyisocyanates may be used alone or in combination of two or more. Asused herein, the terms “combination,” “combination thereof,” and‘combinations thereof’ may refer to a chemical combination (e.g., analloy or chemical compound), a mixture, or a laminated structure ofcomponents.

According to an exemplary embodiment of the present disclosure, thepolyisocyanate may also have a linear structure without a side chain.Therefore, the polymer formed by reacting polyisocyanate with the firstpolyol and the second polyol may have a linear structure. The polymermay be, for example, polyurethane. As described herein, since thepolymer formed by the reaction of the first polyol, the second polyol,and the polyisocyanate has a linear structure, flexibility andwettability of the coating layer made from the resin composition may beimproved. Thus, the coating layer may have an excellent bubble-freeproperty.

According to an exemplary embodiment of the present disclosure, a resincomposition may include about 10 to about 20 parts by weight of thesecond polyol, and about 3 to about 8 parts by weight of thepolyisocyanate, with respect to 100 parts by weight of the first polyol.The reaction amount of the first polyol, the second polyol, and thepolyisocyanate may be controlled by satisfying an above compositionratio of the resin composition. Thus, a coating layer having appropriateor suitable adhesion and a bubble-free property may be formed. When areaction amount of the first polyol, the second polyol, and thepolyisocyanate is less than an appropriate or suitable amount, anadhesion of the coating layer may be lowered. When a reaction amount ofthe first polyol, the second polyol, and the polyisocyanate is more thanan appropriate or suitable amount, an adhesion of the coating layerbecomes excessively large, making it difficult to peel off the coatinglayer from the substrate.

According to an exemplary embodiment of the present disclosure, theresin composition may further include a curing agent and an antistaticagent.

The curing agent aids in curing the resin composition in the aging act.As used herein, the term “act” may be interchanged with the term“stage,” “phase,” or “segment.” For example, the curing agent controls acuring reaction of the resin composition so that the coating layer canhave a suitable mechanical and chemical property. The curing agent mayinclude an isocyanate. The curing agent may include, for example, amixture of dodecanedioic acid and triglycidyl isocyanurate having thefollowing structure.

The dodecanedioic acid and triglycidyl isocyanurate in the curing agentmay be mixed to a weight ratio of about 10:4 to about 10:6. By mixingtriglycidyl isocyanurate with dodecanedioic acid to the above weightratio, the curing reaction rate may be improved. When triglycidylisocyanurate is used alone, the curing reaction rate may be relativelyslow. By using the curing agent including a mixture of triglycidylisocyanurate and dodecanedioic acid, a gloss of the coating layer can bereduced and a light transmittance can be improved.

The curing agent may be added to a ratio of about 0.01 to about 1 partby weight based on 100 parts by weight of the resin composition. Whenthe curing agent is included in an amount of less than about 0.01 partby weight, a curing speed of the resin composition may be significantlydeteriorated. In addition, when the curing agent is included in anamount of more than about 1 part by weight, the coating layer may beexcessively cured, so that flexibility and a bubble-free property of thecoating layer may be deteriorated.

According to an exemplary embodiment of the present disclosure, theantistatic agent may include a compound represented by Chemical Formula3.

M-A  Chemical Formula 3

In Chemical Formula 3, M is a metal element, and A is at least oneselected from a chloride anion (Cl⁻), a bromide anion (Br⁻), an iodideanion (I⁻), a tetrachloroaluminate anion (AlCl₄ ⁻), aheptachlorodialuminate anion (Al₂Cl₇ ⁻), a tetrafluoroborate anion (BF₄⁻), a hexafluorophosphate anion (PF₆ ⁻), a perchlorate anion (ClO₄ ⁻), anitrate anion (NOD, an acetate anion (CH₃COO⁻), a trifluoroacetate anion(CF₃COO⁻), a methane sulfonate anion (CH₃SO₃ ⁻), atrifluoromethanesulfonate anion (CF₃SO₃ ⁻), a p-toluenesulfonate anion(p-CH₃C₆H₄SO₃ ⁻), a bis (fluorosulfonyl) imide anion ((FSO₂₂N⁻), a bis(trifluoromethanesulfonyl) imide anion ((CF₃SO₂)₂N⁻), a tris(trifluoromethanesulfonyl) (CF₃SO₂)₃C⁻), a hexafluoroacenate anion (AsF₆⁻), a hexafluoroantimonate anion (SbF₆ ⁻), a hexafluoroniobate anion(NbF₆ ⁻), a hexafluorotantalate anion (TaF₆ ⁻), dimethylphosphinate(CH₃₂POO⁻), a dicyanamide anion ((CN)₂N⁻), a thiocyanic anion (SCN⁻), aperfluorobutane sulfonate anion (C₄F₉SO₃ ⁻), a bis(pentafluoroethanesulfonyl) imide anion ((C₂F₅SO₂)₂N⁻) and aperfluorobutanoate anion (C₃F₇COO⁻).

The antistatic agent imparts an antistatic property to the coating layerformed from the resin composition. According to an exemplary embodimentof the present disclosure, the antistatic agent may be in a metal-saltform such as Chemical Formula 3. The antistatic agent in the metal-saltform can coordinate with a non-covalent electron pair of an ether group(—O—) in the first polyol. By combining the antistatic agent with thefirst polyol, a thermal stability of the antistatic agent can beimproved. For example, the antistatic property can be ensured even at ahigh temperature of 300° C. or higher, and the antistatic agentcomponent does not transfer to a surface of the coating layer or thesubstrate at the high temperature condition.

An anion of the antistatic agent may include a fluorine atom. Forexample, the anion of the antistatic agent may be at least one selectedfrom a tetrafluoroborate anion (BF₄ ⁻), a hexafluorophosphate anion (PF₆⁻), a trifluoromethanesulfonate anion (CF₃SO₃ ⁻), a bis (fluorosulfonyl)imide anion (FSO₂₂N⁻), a bis (trifluoromethanesulfonyl) imide anion((CF₃SO₂)₂N⁻), a tris (trifluoromethanesulfonyl) methanide anion((CF₃SO₂)₃C⁻), a hexafluoroacetate anion (AsF₆ ⁻), ahexafluoroantimonate anion (SbF₆ ⁻), a hexafluoroniobate anion (NbF₆ ⁻),and a hexafluorotantalate anion (TaF₆ ⁻). Since a fluorine atom hasstrong electronegativity, an antistatic agent having an anion includingthe fluorine atom has an excellent antistatic property.

The antistatic agent may be a lithium-based antistatic agent including alithium element. For example, the lithium-based antistatic agent mayhave a structure of Chemical Formula 3-1.

The lithium-based antistatic agent can coordinate with a non-covalentelectron pair of an ether group (—O—) in the first polyol, therebyimproving thermal stability of the antistatic agent.

The antistatic agent may be included to a ratio of about 0.05 to 0.3parts by weight based on 100 parts by weight of the resin composition.When the antistatic agent is included in an amount of less than about0.05 part by weight, antistatic property may be deteriorated, and whenthe antistatic agent is included in an amount of more than about 0.3part by weight, the number of a bonding between a non-covalent electronpair of an ether group (—O—) in the first polyol and the antistaticagent is excessively increased, so that a mechanical property of thecoating layer may be deteriorated.

The resin composition according to an exemplary embodiment of thepresent disclosure may further include a tin catalyst. The tin catalystmay be an organotin catalyst, for example, and may be at least oneselected from monobutyl tin (MBT), dibutyl tin (DBT), tributyl tin(TBT), tetrabutyl tin (TeBT), mono octyl tin (MOT), dioctyltin (DOT),triphenyltin (TPhT), tricyclohexyltin (TCIT), and dibutyltin dilaulate(DBTDL). The catalyst can promote curing of the resin composition orpromote reaction between the first polyol, the second polyol, and/or thepolyisocyanate.

The catalyst may be included to a ratio of about 0.01 to about 0.5 partsby weight based on 100 parts by weight of the resin composition. Thiscontent of the catalyst is in a range capable of promoting the formationof the coating layer without or substantially without affecting aphysical property of the resin composition or the coating layer.

The resin composition according to an exemplary embodiment of thepresent disclosure may further include at least one solvent selectedfrom the group consisting of toluene, acetone, cyclohexanone, ethylcellusolve, ethyl acetate, isopropyl alcohol, and ethylene glycolmonomethyl ether.

According to an exemplary embodiment of the present disclosure, thefirst polyol, the second polyol, and the polyisocyanate may be mixedwith a first solvent, and the curing agent and antistatic agent may bemixed with a second solvent different from the first solvent. Themixture of the first polyol, the second polyol, and the polyisocyanateand the first solvent, and the mixture of the curing agent and theantistatic agent and the second solvent may then be mixed.

The reason why the first polyol, the second polyol, and thepolyisocyanate, and the curing agent and the antistatic agent are mixedin different solvents is to suppress or reduce a side reaction by thecuring agent. For example, when the first polyol, the second polyol, thepolyisocyanate, and the curing agent are mixed at the same orsubstantially the same time, a side reaction may occur between the firstpolyol and/or the second polyol and the curing agent. This side reactioncan reduce an amount of reaction between the first polyol, the secondpolyol and/or the polyisocyanate.

According to an exemplary embodiment of the present disclosure, theresin composition may further include a heat stabilizer, and the heatstabilizer may be a phenolic compound, a phospho compound, or a thiocompound. The heat stabilizer improves heat resistance of the resincomposition. By adding the heat stabilizer into the resin composition,the first polyol, the second polyol, the polyisocyanate, and a linearpolymer formed by reaction thereof in the resin composition can beprevented from thermally decomposing at a high temperature (or alikelihood or amount of such decomposition may be reduced). The heatstabilizer may be included to a ratio of about 0.001 to about 0.6 partsby weight based on 100 parts by weight of the resin composition.

FIG. 1 is a flowchart illustrating a manufacturing method of a coatinglayer according to an exemplary embodiment of the present disclosure. Inaddition, FIG. 2 is a flowchart illustrating a method of forming a resincomposition according to an exemplary embodiment of the presentdisclosure.

Referring to FIG. 1, a manufacturing method of a coating layer accordingto an exemplary embodiment of the present disclosure includes forming aresin composition (S100), coating the resin composition (S200), andaging the resin composition (S300).

Referring to FIG. 2, the forming a resin composition (S100) may includemixing a first polyol, a second polyol, a polyisocyanate and a firstsolvent (S110), heating a mixture and removing an isocyanate bond(S120), mixing a heat stabilizer (e.g., adding a heat stabilizer to themixture) (S130), and mixing a second solvent, a curing agent, and anantistatic agent to the mixture (e.g., adding a second solvent, a curingagent, and an antistatic agent to the mixture) (S140).

Hereinafter, acts of the manufacturing method of the coating layer willbe described in more detail.

First, in the forming a resin composition (S100), the first polyol, thesecond polyol, the polyisocyanate, and the first solvent are mixed(S110). The matters relating to the first polyol, the second polyol, thepolyisocyanate, and the first solvent are as described herein. Thesematerials may be mixed with stirring at room temperature. At this time,a mixing temperature and method may change depending on the specificmaterial used.

The mixture formed by mixing the first polyol, the second polyol, thepolyisocyanate, and the first solvent is heated (S120). By heating themixture, an isocyanate bond (—NCO) in the mixture may be removed (e.g.,the isocyanate group (—NCO) may react with a hydroxyl group). At thistime, the mixture may be heated to a temperature of about 60° C. toabout 90° C. This temperature range is a temperature range in which thefirst polyol, the second polyol, the polyisocyanate, and the linearpolymer formed by the reaction thereof are not pyrolyzed while removingthe isocyanate bond (e.g., while reacting the isocyanate bond, forexample, with a hydroxyl group). When the mixture is heated to atemperature less than about 60° C., the isocyanate bond may not besufficiently or suitably removed, and when the mixture is heated to atemperatures more than about 90° C., the first polyol, the secondpolyol, the polyisocyanate, and the linear polymer formed by thereaction thereof may be pyrolyzed.

After removing the isocyanate bond, a heat stabilizer may be added tothe mixture (S130). The matters relating to the heat stabilizer are asdescribed herein. The heat stabilizer imparts thermal stability to theresin composition so that the linear polymer formed by the reaction ofthe first polyol, the second polyol, and the polyisocyanate is notpyrolyzed in the subsequent aging act. When the heat stabilizer is addedbefore removing the isocyanate bond, the isocyanate bond may not beremoved due to action of the heat stabilizer. Therefore, the heatstabilizer may be added after heating for removing (e.g., reacting) theisocyanate group.

After mixing (e.g., adding) the heat stabilizer to the mixture, a secondsolvent, a curing agent, and an antistatic agent may be added to themixture (S140). At this time, the second solvent, curing agent, andantistatic agent may be premixed before being added to the mixture. Thereason why the second solvent, the curing agent, and the antistaticagent are added after mixing in a separate act is to prevent the curingagent from reacting with the first polyol or the second polyol asdescribed herein (or to reduce a likelihood or amount of such reaction).

The formed resin composition is coated on a substrate (S200). The amountof the resin composition to be coated may change depending on acomposition of the resin composition and a type of the substrate. Theresin composition may be coated on the substrates by a method such as agravure coating, a roll coating, a comma coating, an air knife coating,a kiss coating, a spray coating, a suspension coating, an immersioncoating, a spinner coating, a wheeler coating, a brushing, a frontcoating by a silk screen, a wire bar coating, a flow coating, an offsetprinting, a letterpress printing, and the like. However, the coatingmethod of the resin composition described herein is merely exemplary,and a person skilled in the art may coat the resin composition on thesubstrate by using an appropriate or suitable method in addition to themethod listed above.

The substrate may be a window of a display device. The substrate may bemade of at least one material selected from the group consisting ofglass, aluminosilicate (e.g., aluminosilicate glass), borosilicate(e.g., borosilicate glass), and boroaluminosilicate (e.g.,boroaluminosilicate glass). However, a material of the substrate is notlimited to the materials listed above. In the case where the substrateis a window of a display device, a material having good durability andexcellent surface smoothness and transparency in addition to thematerials listed above may be used as a substrate.

The substrate may have flexibility. The substrate having flexibility maybe bent or folded if necessary or desired. In this case, the substratemay have relatively small bending stiffness so that it can be bent orfolded easily. The substrate may have various suitable shapes such as arectangle, a square, a circle, an ellipse, a semicircle, a half ellipse,and/or the like.

In the case where the substrate includes glass, the substrate mayinclude an ion-exchanged chemically strengthened layer (e.g., a chemicaltempered layer). The chemical tempered layer may be formed by performinga chemical strengthening treatment on an outer surface of the substrate.The chemical strengthening treatment may include an ion exchangeprocess. In the ion exchange process for the chemical tempered layer, acation disposed at or near surface of glass at a temperature lower thana strain point of a substrate is exchanged with another cation of thesame valence. For example, alkali metal cations such as Na+ and Li+ inthe glass may be exchanged with cations such as K+ by the ion exchangeprocess. The ion exchange process may include the act of supporting thesubstrate in an ion exchange salt and heating the supported substrate.The ion exchange salt includes ions to be exchanged with ions in thesubstrate. The ions included in the ion exchange salt may be K+, andions in the substrate to be exchanged may be Na+ or Li+. The ionexchange salt may be in a nitrate form. When the substrate supported inthe ion exchange salt is heated, the ions in the ion exchange saltdiffuse through the surface of the substrate. The substrate may beheated at or to a temperature of about 370° C. to about 450° C. for atime period of about 1 hour to about 6 hours.

As the chemically strengthened layer is formed on the substrate, bendingrigidity of the substrate is decreased and the substrate and protectivecover 100 may be bent or folded more easily. The chemically strengthenedlayer may provide a compressive stress profile extending from a surfaceof the substrate to a set or specific position of the substrate to thesubstrate

The chemical strengthening treatment may be performed on one side orboth sides of the substrate. In addition, the chemical strengtheningtreatment may be performed symmetrically or asymmetrically on a frontand back sides of the substrate. In the case where the substrate ismainly folded in a set or specific direction, the chemical strengtheningtreatment may be performed asymmetrically. For example, in the casewhere the substrate is mainly folded in only one direction, compressivestress may be applied to a surface in which both ends face each other,and tensile stress may be applied to a surface opposite to the surface.In the case where a type of stress mainly applied to both sides of thesubstrate is different as described herein, the chemical strengtheningtreatment may be performed asymmetrically.

The coated resin composition may be aged (S300). Aging includes curingand refers to a process for promoting the reaction between components inthe resin composition. The aging may be performed at a temperature ofabout 40° C. to about 140° C. When the aging temperature is less thanabout 40° C., the reaction between the components in the resincomposition may not be suitable or sufficient. In addition, when theaging temperature is more than about 140° C., the components in theresin composition may be pyrolyzed. The pyrolyzed material may reactwith a surface of the substrate to contaminate the surface of thesubstrate.

According to an exemplary embodiment of the present disclosure, aging ofthe resin composition may include a plurality of heating acts. Inaddition, in the plurality of heating acts, the resin composition may beheated to different temperatures. This is because the resin compositionincludes a large amount of organic materials. The properties of organicmaterials may change when the organic materials are heated from a lowtemperature to a high temperature for a short time. For example, when anorganic material at a room temperature is placed in a heating chamber at140° C., the organic material may be burned or pyrolyzed without beingable to withstand abrupt temperature change. Therefore, when arelatively high temperature process is required for the aging, the resincomposition should be slowly heated.

According to an exemplary embodiment of the present disclosure, aplurality of heating acts may have different process temperatures andthe process temperature of the heating act may sequentially increaseaccording to the process sequence.

The number of heating acts of the aging act may change depending on thecomposition of the resin composition. According to an exemplaryembodiment of the present disclosure, the aging act may include a firstheating act, a second heating act, a third heating act, a fourth heatingact, a fifth heating act, and a sixth heating act, which aresequentially performed.

FIG. 3 shows an aging apparatus for performing a first heating act 101,a second heating act 102, a third heating act 103, a fourth heating act104, a fifth heating act 105, and a sixth heating act 106. In the agingapparatus, the resin composition and the substrate proceed from thefirst heating act 101 to the sixth heating act 106.

As described herein, as the resin composition may be denatured by rapidheating, the process temperature of the first heating act 101 to thesecond heating act 102 in the front of the aging act may be lower thanthe process temperature of the third heating act 103 to the fifthheating act 105. In addition, the process temperature of the sixthheating act 106 may be lower than the process temperature of the thirdheating act 103 to the fifth heating act 105 to prevent abrupttemperature change of a coating layer (or to reduce a likelihood oramount of such temperature change).

After the resin composition is aged, a coating layer is formed on thesubstrate. Another film may be stacked on the coating layer if necessaryor desired. For example, a hard coating film, an anti-fingerprint film,an anti-reflection film, or the like may be stacked on the coatinglayer.

Since the coating layer has excellent adhesion, these films may bestably bonded on the substrate. However, since the coating layeraccording to embodiments of the present disclosure has peelability,films which are stacked on the substrate and between which the coatinglayer interposed may be peeled and then reattached if necessary ordesired. Even when these films are peeled and then reattached, bubblesare not inserted or formed between the substrate and the coating layer.This is because the coating layer according to embodiments of thepresent disclosure has an excellent bubble-free property. Therefore,even when the films are peeled and then reattached to the substrate, thesubstrate and the films and the coating layer are in close contact witheach other, thereby having excellent adhesion even after being peeledand reattached.

Hereinafter, the physical property of the resin composition according toExamples of embodiments of the present disclosure and ComparativeExamples were tested.

Example 1

About 100 parts by weight of polypropylene glycol, about 12 parts byweight of polyether glycol, about 0.02 parts by weight of dibutyltindilaurate, about 6 parts by weight of hexamethylene diisocyanate andabout 66.78 parts by weight of toluene were mixed in a four-neckedflask, and then the temperature was raised to about 80° C. After about 3hours of reaction, it was confirmed by IR equipment that no residualisocyanate groups were present. Then, about 0.3 part by weight of a heatstabilizer (benzene propanoic acid,3,5-(1,1-dimethylethyl)-4-hydroxy-2,1-ethanedilester) was added and thereaction was terminated.

5 parts by weight of an isocyanate curing agent (hexamethylenediisocyanate trimer), 0.12 parts by weight of a lithium salt antistaticagent and 100 parts by weight of toluene were mixed with 100 parts byweight of the mixture in which the reaction was terminated to preparethe resin composition of Example 1.

Comparative Example 1

About 100 parts by weight of polymethylsiloxane and about 2.1 parts byweight of a silicone oil were mixed, and then about 2 parts by weight ofa crosslinking agent (2,5-dimethyl-2,5-bis (tert-butylperoxy)-hexane)was mixed with about 100 parts by weight of a mixture of thepolymethylsiloxane and the silicone oil to prepare the resin compositionof Comparative Example 1.

(Evaluation of Physical Property)

The resin compositions of Example 1 and Comparative Example 1 werecoated on a PET film to a thickness of about 50 μm, and aged to form acoating layer. Bubble-free property, adhesion, antistatic property,reliability under high-temperature/high-humidity condition, surfaceenergy, and glass surface contamination were measured for the coatinglayers prepared from the respective resin composition of Example 1 andComparative Example 1.

When a coating layer having a size of 63 mm×111 mm was formed on thesubstrate and the coating layer was peeled and then reattached, thebubble-free property was obtained by measuring a time taken to removebubble inserted or formed in a region from a center of the coating layerto both ends of the coating layer. The time taken to remove the bubblewas measured five times, and the time described herein is an average offive measurements. The shorter the time taken to remove the bubble, theless bubble is (or the fewer bubbles are) inserted or formed between thesubstrate and the coating layer, and the bubble can be easily removed.Therefore, the bubble-free property is excellent for coating layers thathave a short time to remove the bubbles.

The adhesion between the coating layer and the glass was measured at ahead speed of 150 mm/min using UTM (Universal Testing Machine:DTU-900MHA). The adhesion was measured three times, and the adhesiondescribed herein is an average of three measurements. Since the coatinglayer and the substrate according to embodiments of the presentdisclosure may be repeatedly peeled and reattached to each other, theadhesion of the coating layer may be at an appropriate or suitablelevel. Herein, the appropriate or suitable level may change according tothe kind of substrate, and may be from about 1.0 gf/in to about 3.0gf/in for a glass substrate.

The antistatic property was obtained by measuring surface resistance ofthe coating layer using a resistance meter. The antistatic property wasmeasured three times, and the surface resistance described herein is anaverage of three measurements. The lower the surface resistance of thecoating layer, the better the antistatic property.

The reliability at a high temperature and high humidity condition isobtained by measuring physical property of the coating layer afterforming the coating layers using the respective resin composition ofExample 1 and Comparative Example 1 and then leaving the coating layerat a high temperature and high humidity condition for a long time. Thereliability of the coating layers at a high temperature and highhumidity condition was measured after leaving the coating layers at atemperature of about 60° C. and a humidity of about 93% for about 120hours, and after leaving the coating layers at a temperature of about85° C. and a humidity of about 85% for about 120 hours. The reliabilityevaluation was obtained by measuring the physical property of thecoating layer subjected to the high temperature and high humiditycondition over three days. The measured physical properties are thebubble-free property, the adhesion, the antistatic property, the surfaceenergy, and the glass surface contamination of the coating layer.

The surface energy property was obtained by measuring the surfacetension of the coating layer. That is, the surface energy property wasobtained by measuring a surface tension of an ink layer by using a Dynepen on the surface of the coating layer.

The glass surface contamination was obtained by checking whether thecoating layer or the resin composition remains on the glass surface whenthe coating layer is peeled after the coating layer is formed on theglass. The glass surface contamination was visually checked under a3-wavelength lamp and rated 0 to 5.

Hereinafter, the physical property evaluation value of the coating layerformed using the resin compositions of Example 1 and Comparative Example1 is shown. Table 1 shows the physical property of the resin compositionof Example 1 and Comparative Example 1 before and after reliabilityevaluation. The reliability evaluation condition is for about 120 hoursat a temperature of about 60° C. and a humidity of about 93%.

TABLE 1 Bubble-free property Adherence Antistatic property Surfaceenergy Glass surface contamination Comparative Comparative ComparativeComparative Comparative Example 1 Example 1 Example 1 Example 1 Example1 Example 1 Example 1 Example 1 Example 1 Example 1 Before  1.1 sec 1.25sec 1.6 gf/in 1.8 gf/in  10⁹ Ω/m² 10¹² Ω/m² 38 dyne/cm 38 dyne/cm 0 0applying reliability evaluation condition 1 day after 1.18 sec 1.42 sec1.3 gf/in 1.9 gf/in 10^(8.6) Ω/m² 10¹² Ω/m² 38 dyne/cm 32 dyne/cm 0 1applying reliability evaluation condition 2 day after 1.21 sec 1.33 sec1.5 gf/in 1.8 gf/in 10^(9.2) Ω/m² 10¹² Ω/m² 38 dyne/cm 30 dyne/cm 0 2applying reliability evaluation condition 3 day after 1.28 sec 1.28 sec1.7 gf/in 1.6 gf/in 10^(8.8) Ω/m² 10¹² Ω/m² 40 dyne/cm 31 dyne/cm 0 2applying reliability evaluation condition

Hereinafter, the physical property evaluation values of the coatinglayers formed using the respective resin compositions of Example 1 andComparative Example 1 are shown. Table 2 shows the physical property ofthe resin composition of Example 1 and Comparative Example 1 before andafter reliability evaluation. The reliability evaluation condition isfor about 120 hours at a temperature of about 85° C. and a humidity ofabout 85%.

TABLE 2 Bubble-free property Adhesion Antistatic property Surface energyGlass surface contamination Comparative Comparative ComparativeComparative Comparative Example 1 Example 1 Example 1 Example 1 Example1 Example 1 Example 1 Example 1 Example 1 Example 1 Before  1.1 sec 1.25sec 1.6 gf/in 1.6 gf/in  10⁹ Ω/m² 10¹² Ω/m² 38 dyne/cm 38 dyne/cm 0 0applying reliability evaluation condition 1 day after  1.2 sec 1.44 sec1.8 gf/in 2.5 gf/in 10^(8.6) Ω/m² 10¹² Ω/m² 39 dyne/cm 35 dyne/cm 0 2applying reliability evaluation condition 2 day after 1.32 sec 1.45 sec1.8 gf/in 2.8 gf/in 10^(8.7) Ω/m² 10¹² Ω/m² 37 dyne/cm 32 dyne/cm 0 3applying reliability evaluation condition 3 day after 1.35 sec 1.32 sec2.5 gf/in 2.9 gf/in 10^(9.0) Ω/m² 10¹² Ω/m² 38 dyne/cm 30 dyne/cm 0 3applying reliability evauation condition

It was confirmed that the coating layer formed from the resincomposition of Example 1 was excellent in the bubble-free property, theantistatic property, the surface energy and the glass surfacecontamination and both before and after the reliability evaluation. Inthe evaluation of the adhesion, all the coating layers formed from therespective resin composition of Example 1 and Comparative Example 1 hadthe adhesion in a range of about 1.0 gf/in to about 3.0 gf/in.Therefore, it was confirmed that all the coating layers formed from therespective resin compositions of Example 1 and Comparative Example 1were suitable for repeated peeling and bonding.

(Evaluation of Aging Condition)

With respect to the resin composition of Example 1, the physicalproperty of the coating layer was evaluated while changing a processtemperature in the heating act of the aging act. The evaluated physicalproperties are bubble-free property, adhesion, antistatic property,surface energy, and glass surface contamination. The aging act includessix sequential heating acts, and the process temperatures in each actare shown in Table 3 below. That is, coating layers of Example 2,Comparative Example 2, and Comparative Example 3 were prepared byheating a coating layer prepared according to Example 1 as set forth inTable 3.

TABLE 3 First Second Third Fourth Fifth Sixth heating act heating actheating act heating act heating act heating act Example 2 30-40° C.80-90° C. 100-110° C. 120-140° C. 110-130° C. 70-80° C. Comparative15-25° C. 30-40° C.  60-70° C.  90-100° C. 110-120° C. 60-70° C. Example2 Comparative 70-80° C. 90-100° C.  110-120° C. 120-140° C. 160-150° C.80-90° C. Example 3

Hereinafter, the physical property evaluation according to Example 2 andComparative Examples 2 and 3 is shown. Table 4 and Table 5 show a resultof performing reliability evaluation for about 120 hours at atemperature of about 60° C. and a humidity of about 93%, and Table 6 andTable 7 shows a result of performing reliability evaluation for about120 hours at a temperature of about 85° C. and a humidity of about 85%.

TABLE 4 Bubble-free property Adhesion Antistatic property Surface energyGlass surface contamination Comparative Comparative ComparativeComparative Comparative Example 2 Example 2 Example 2 Example 2 Example2 Example 2 Example 2 Example 2 Example 2 Example 2 Before  1.1 sec 4.25sec 1.6 gf/in  5.5 gf/in  10⁹ Ω/m²  10⁹ Ω/m² 38 dyne/cm 38 dyne/cm 0 0applying reliability evaluation condition 1 day after 1.18 sec 5.55 sec1.3 gf/in  9.8 gf/in 10^(8.6) Ω/m² 10^(8.8) Ω/m² 38 dyne/cm 35 dyne/cm 03 applying reliability evaluation condition 2 day after 1.21 sec  8.8sec 1.5 gf/in 12.5 gf/in 10^(9.2) Ω/m² 10^(9.3) Ω/m² 38 dyne/cm 33dyne/cm 0 5 applying reliability evalution condition 3 day after 1.28sec 12.11 sec  1.7 gf/in 23.7 gf/in 10^(8.8) Ω/m² 10^(9.0) Ω/m² 40dyne/cm 33 dyne/cm 0 5 applying reliability evaluation condition

TABLE 5 Bubble-free property Adhesion Antistatic property Surface energyGlass surface contamination Comparative Comparative ComparativeComparative Comparative Example 2 Example 3 Example 2 Example 3 Example2 Example 3 Example 2 Example 3 Example 2 Example 3 Before  1.1 sec 2.21sec 1.6 gf/in 2.8 gf/in  10⁹ Ω/m² 10^(9.2) Ω/m² 38 dyne/cm 38 dyne/cm 00 applying reliability evaluation condition 1 day after 1.18 sec 2.55sec 1.3 gf/in 2.9 gf/in 10^(8.6) Ω/m² 10^(8.5) Ω/m² 38 dyne/cm 36dyne/cm 0 2 applying reliability evaluation condition 2 day after 1.21sec 3.11 sec 1.5 gf/in 2.1 gf/in 10^(9.2) Ω/m² 10^(9.5) Ω/m² 38 dyne/cm34 dyne/cm 0 2 applying reliability evaluation condition 3 day after1.28 sec 2.85 sec 1.7 gf/in 2.3 gf/in 10^(8.8) Ω/m² 10^(8.9) Ω m² 40dyne/cm 34 dyne/cm 0 2 applying reliability evaluation condition

TABLE 6 Bubble-free property Adhesion Antistatic property Surface energyGlass surface contamination Comparative Comparative ComparativeComparative Comparative Example 2 Example 2 Example 2 Example 2 Example2 Example 2 Example 2 Example 2 Example 2 Example 2 Before  1.1 sec 4.25sec 1.6 gf/in  5.5 gf/in  10⁹ Ω/m²  10⁹ Ω/m² 38 dyne/cm 38 dyne/cm 0 0applying reliability evaluation condition 1 day after  1.2 sec 6.33 sec1.8 gf/in 10.21 gf/in 10^(8.6) Ω/m² 10^(8.6) Ω/m² 39 dyne/cm 33 dyne/cm0 5 applying reliability evaluation condition 2 day after 1.32 sec 9.21sec 1.8 gf/in 15.78 gf/in 10^(8.7) Ω/m² 10^(9.2) Ω/m² 37 dyne/cm 32dyne/cm 0 5 applying reliability evaluation condition 3 day after 1.35sec 14.56 sec  2.5 gf/in 29.22 gf/in 10^(9.0) Ω/m² 10^(9.0) Ω/m² 38dyne/cm 32 dyne/cm 0 5 applying reliability evaluation condition

TABLE 7 Bubble-free property Adhesion Antistatic property Surface energyGlass surface contamination Comparative Comparative ComparativeComparative Comparative Example 2 Example 3 Example 2 Example 3 ExampIe2 Example 3 Example 2 Example 3 Example 2 Example 3 Before  1.1 sec 2.21sec 1.6 gf/in 1.6 gf/in  10⁹ Ω/m² 10^(9.2) Ω/m² 38 dyne/cm 38 dyne/cm 00 applying reliability evaluation condition 1 day after  1.2 sec 2.35sec 1.8 gf/in 2.5 gf/in 10^(8.6) Ω/m² 10^(8.7) Ω/m² 39 dyne/cm 36dyne/cm 0 2 applying reliability evaluation condition 2 day after 1.32sec 3.88 sec 1.8 gf/in 2.8 gf/in 10^(8.7) Ω/m  10^(9.2) Ω/m² 37 dyne/cm34 dyne/cm 0 2 applying reliability evaluation condition 3 day after1.35 sec 3.55 sec 2.5 gf/in 2.9 gf/in 10^(9.0) Ω/m² 10^(9.0) Ω/m² 38dyne/cm 34 dyne/cm 0 2 applying reliability evaluation condition

Referring to Tables 4 to 7, it can be confirmed that Example 2 exhibitsexcellent physical property under two reliability evaluation conditions.Thus, it can be confirmed that maintaining the process temperature ofabout 100° C. to about 140° C. in the third to fifth heating act,maintaining the process temperature of about 30° C. to about 40° C. inthe first heating act, and maintaining the process temperature of about70° C. to about 90° C. in the second and sixth heating act are anoptimized aging condition.

Table 8 shows adhesion data of the coating layer for aged day (e.g.,aged for a number of days) according to embodiments of the presentdisclosure. The adhesion was evaluated at about 60° C.

TABLE 8 Aged day Adhesion 0 39.00 gf/in 1 2.73 gf/in 2 1.64 gf/in 3 1.42gf/in 4 1.33 gf/in 5 1.45 gf/in 6 1.61 gf/in 7 1.43 gf/in

Referring to Table 8, it can be confirmed that the adhesion of thecoating layer decreases as the number of aged day increases. Asdescribed herein, since the coating layer according to embodiments ofthe present disclosure must ensure peeling and reattachment of thecoating layer and the substrate, the coating layer may have an adhesionof about 1.0 gf/in to about 3.0 gf/in. According to Table 8, the coatinglayer may have more than one day of aging to control the adhesion.

While the subject matter of the present disclosure has been shown anddescribed with reference to certain exemplary embodiments thereof, itwill be understood by those skilled in the art that various changes inform and details may be made therein without departing from the spiritand scope of the present disclosure as defined by the appended claimsand their equivalents.

Accordingly, the technical scope of the present disclosure may bedetermined by on the technical scope of the accompanying claims.

DESCRIPTION OF SOME OF THE SYMBOLS

-   101-106: first heating act-sixth heating act

What is claimed is:
 1. A resin composition comprising: a first polyolrepresented by Chemical Formula 1; a second polyol represented byChemical Formula 2; and a polyisocyanate, wherein the first polyol andthe second polyol have a linear structure without a side chain,

wherein, in Chemical Formula 1 and Chemical Formula 2, each of Y₁ to Y₄is H or OH—, at least one selected from Y₁ and Y₂ is OH—, at least oneselected from Y₃ and Y₄ is OH—, each of X₁ to X₃ is independentlyselected from a C₁-C₂₀ alkyl group not including an unsaturated bond,and a C₁-C₂₀ alkyl group including an unsaturated bond, —CH₂— in thealkyl group may be substituted or unsubstituted with —CHOH—, and each ofn and m is independently 1 to
 200. 2. The resin composition of claim 1,further comprising: a curing agent and an antistatic agent, wherein thecuring agent comprises isocyanate.
 3. The resin composition of claim 2,wherein: the curing agent comprises a mixture of dodecanedioic acid andtriglycidyl isocyanurate.
 4. The resin composition of claim 2, wherein:the antistatic agent comprises a compound represented by ChemicalFormula 3,M-A  Chemical Formula 3 wherein, in Chemical Formula 3, M is a metalelement, and A is at least one selected from a chloride anion (Cl⁻), abromide anion (Br⁻), an iodide anion (I⁻), a tetrachloroaluminate anion(AlCl₄ ⁻), a heptachlorodialuminate anion (Al₂Cl₇ ⁻), atetrafluoroborate anion (BF₄ ⁻), a hexafluorophosphate anion (PF₆ ⁻), aperchlorate anion (ClO₄ ⁻), a nitrate anion (NO₃ ⁻), an acetate anion(CH₃COO⁻), a trifluoroacetate anion (CF₃COO⁻), a methane sulfonate anion(CH₃SO₃ ⁻), a trifluoromethanesulfonate anion (CF₃SO₃ ⁻), ap-toluenesulfonate anion (p-CH₃C₆H₄SO₃ ⁻), a bis (fluorosulfonyl) imideanion ((FSO₂₂N⁻), a bis (trifluoromethanesulfonyl) imide anion((CF₃SO₂)₂N⁻), a tris (trifluoromethanesulfonyl) (CF₃SO₂)₃C⁻), ahexafluoroacenate anion (AsF₆ ⁻), a hexafluoroantimonate anion (SbF₆ ⁻),a hexafluoroniobate anion (NbF₆ ⁻), a hexafluorotantalate anion (TaF₆⁻), dimethylphosphinate (CH₃₂POO⁻), a dicyanamide anion ((CN)₂N⁻), athiocyanic anion (SCN—), a perfluorobutane sulfonate anion (C₄F₉SO₃ ⁻),a bis (pentafluoroethanesulfonyl) imide anion ((C₂F₅SO₂)₂N⁻) and aperfluorobutanoate anion (C₃F₇COO⁻).
 5. The resin composition of claim4, wherein: the antistatic agent is a lithium-based antistatic agentcomprising a lithium element.
 6. The resin composition of claim 1,further comprising: a tin-based catalyst.
 7. The resin composition ofclaim 1, wherein: the second polyol is present in an amount of about 10to about 20 parts by weight, and the polyisocyanate is present in anamount of about 3 to about 8 parts by weight, based on 100 parts byweight of the first polyol.
 8. The resin composition of claim 1, furthercomprising: at least one solvent selected from the group consisting oftoluene, acetone, cyclohexanone, ethyl cellusolve, ethyl acetate,isopropyl alcohol, and ethylene glycol monomethyl ether.
 9. The resincomposition of claim 1, further comprising: a heat stabilizer, whereinthe heat stabilizer comprises a phenolic compound, a phospho compound,or a thio compound.
 10. A method of manufacturing a coating layer, themethod comprising: forming a resin composition by mixing a first polyolrepresented by Chemical Formula 1, a second polyol represented byChemical Formula 2, and a polyisocyanate together with a first solvent;coating the resin composition on a substrate; and aging the resincomposition, wherein the first polyol and the second polyol have alinear structure without a side chain,

wherein, in Chemical Formula 1 and Chemical Formula 2, each of Y₁ to Y₄is H or OH—, at least one of Y₁ and Y₂ is OH—, at least one of Y₃ and Y₄is OH—, each of X₁ to X₃ is independently selected from an unsubstitutedC₁-C₂₀ alkyl group, and a C₁-C₂₀ alkyl group substituted with at leastone selected from an unsaturated bond, —CH₂— in the alkyl group may besubstituted or unsubstituted with —CHOH—, and each of n and m isindependently 1 to
 200. 11. The manufacturing method of a coating layerof claim 10, wherein forming the resin composition further comprisingmixing a mixture of a second solvent different from the first solvent, acuring agent and an antistatic agent mixture with a mixture of the firstpolyol, the second polyol, the polyisocyanate and the first solvent. 12.The manufacturing method of a coating layer of claim 11, furthercomprising heating the mixture of the first polyol, the second polyol,the polyisocyanate and the first solvent to remove isocyanate bonds inthe mixture of the first polyol, the second polyol, the polyisocyanate,and the first solvent.
 13. The manufacturing method of a coating layerof claim 12, wherein the mixture of the first polyol, the second polyol,the polyisocyanate and the first solvent is heated at about 60° C. toabout 90° C.
 14. The manufacturing method of a coating layer of claim13, wherein a heat stabilizer is added to the heated mixture of thefirst polyol, the second polyol, the polyisocyanate and the firstsolvent.
 15. The manufacturing method of a coating layer of claim 10,wherein the aging the resin composition includes heating the resincomposition at about 40° C. to about 140° C.
 16. The manufacturingmethod of a coating layer of claim 10, wherein the aging the resincomposition includes a plurality of heating acts.
 17. The manufacturingmethod of a coating layer of claim 16, wherein The aging the resincomposition includes a first heating act to a sixth heating act whichare sequentially performed.
 18. The manufacturing method of a coatinglayer of claim 17, wherein a process temperature of the first heatingact, the second heating act and the sixth heating act is less than aprocess temperature of the third heating act to the fifth heating act.